Pyrazolone couplers fob color



Reissued June 1, 1943 PYRAZOLONE COUPLERS FOR COLOR PHOTOGRAPKY Henry 1). Porter and Arnold ,Welssherger. Rochester,

pauy, Rochester, N. Y.,

Jersey No Drawing. Original No. 2,311,082, dated Feb- N. Y.. assignors to Eastman Kodak (30ma corporation of New ruaryld, 1943, Serial No. 419,173, November 14, 1941. Application for reissue March 31. 1943, Serial No. 481,354 v 10 Claims. (01. 95-6) This invention relates to photographic color.

forming compounds and particularly to pyramlone color iormin'; coupler compounds.

The formation oi colored photographic images by coupling the development product of aromatic amino developing agents with color forming or coupling compounds is well known. In these processes the subtractive process of color formation is ordinarily used and the image dyes are intended to be or the complementary primary colors cyan or blue-green, magenta, and yellow.

'- The couplers which produce the cyan dyes are usually phenols or naphthols. those producing the magenta dyes are ordinarily pyrazolones or v cyano acetyl compounds, and those producing the yellow dyes are ordinarily compounds containing'a methylene group having two carbonyl groups attached to it. The dyes produced by coupling are azomethines, indamines or indophenols depending upon the composition or the coupler and oi the developer.

We have now iound a novel type oi pyrazolone coupler which produces dyes having good absorption characteristics and good stability. These couplers have the following general formula:

Q /T still R C- HI where R. =alkyl or aryl R'=H, alkyl, or acyl The iolowing examples illustrate compounds of this general class:

O (1) ms HI 3-anilino-5-pyrasolone cmco-s HI 1-acetyl-3-anilino-5-pyrasolone fi-CH: 0 3-a-naphthylamino-5pyrazolone (and l-acetyl derivative) 3-p-acetaminoanillno 5-pyrazolone 3=o-bromanilino-5-pyrazolone (and l-acetyl derivative) macaw-Om 0- HI ll 3-p-hromanilino-5-pyrazolone (and l-acetyl derivative) ran-msG-cn 3- -cyanoanilino-5-pyrazolone (and l-acetyl deriyative) page 2832. An isothiocyanate is condensed with c-crn l 5 3-p-nitroaniline-5-pyrazolone V /N=C-NHC5H11 C- H: 3-n-amylamino-5-pyrazo1one m) I N=CNHOI HN/ l z-0H.

3-p-iodoani1ino-5-pyrazolone "(and l-acetyl de- 'rivative) v (12 N=CNHCiBr CIHICO-N C- H: ii 1-n-valeryl-3-anilino-5-pyrazolone (13) N=CNHC|Hn 30,

i|I|3-GHI 3-p-tert. amylanilino-5-pyrazolone N=CNHON(CH3)I 14 HN/ l C Hr 40 g 3-p-dimethylaminoanilino-5-pyrazolone N=c-N1r-c.m (l5) c.n.co-N

C H] i. 1 benzoyl 3-anilino-5pyramlone N=CNHCHJ (1e) O-wcmco-n o I-phenoxyacetyl-3-anilino-5-pyrazolone N=c-Nnc.m 11) cur-o om co-n I? on U 1-methoxyacetyl-3-anilino-5-pyrazolone N=C-NHO 1a) cm1v I C-CHa ii 1-methy1-3-a nilino-5 pyrazolone. m

The novel couplers of our invention are prepared by a modification of the procedure described in Journal of the American Chemical Society, vol. 44, 1924, page 1551 and vol. 46, 1926,

etbylacetoacetate and the product is reacted with hydrazine hydrate or an aikylhydrazine according to the following general scheme:

RNCS+CHIC O CHrC OaCrHH'NBO ET comm CHIC 0-0 a By variation of the group attached to the amino nitrogen in the 3-position of the pyrazolone ring couplers may be prepared which have the required solubility and other properties for use in various methods oi color photography. Furthermore, the couplers can be acylated by reaction with an organic acid anhydride or by-an acid chloride in the presence 01 a condensing agent such as pyridine. This aflords another means of varying the properties of the couplers.

Our couplers are designed for use in processes in which the coupler is incorporated in the developing solution such as those described in Mannes and Godowsky U. S. Patent 2,113,329, granted April 5. 1938, or Marines, Godowsky a Wilder U. S. Patent 2,252,718, granted August 19, 1941. Certain oi the couplers of our invention may be incorporated in sensitive emulsion layers for use in processes. such as those described in Fischer U. 8. Patent 1,055,155, granted March 4, 1913, Mannes 5: Godowsky U. S. Patents 2,304,939 and 2,304,940, granted December 15, 1942, and Jelley and Vittum U. S. application Serial No. 371,612, died December 26, 1940.

, The following examples illustrate developing Y solutions containing the couplers used according to our invention:

Example 1 A. 2-amino 5 diethylaminotoluene hydrochloride -grams 2 Sodium sulfite (anhydrous) do 2 Sodium carbonate (anhydrous) do 20 Potassium bromide -1. e do' 1 Water to liter 1 B. 3-anilino-5-pyrazolone grams 2 Sodium hydroxide (10% solution) cc 10 His added to A. 1

Example 2 A. Dimethyl-p-phenylenediamine sulfate grams 3 Sodium sulflte (anhydrous) do- 5 Sodium carbonate (anhydrous) do 20 Potassium bromide do 2 Water to liter 1 B. 3-n-amylamino-5-pyrazolone grams 3 Isopropyl alcohol; cc B is added to A. I

The foregoing examples-refer to the addition of the coupler compound to the developing solution itself. The coupler may also be added to the emulsion layer provided that suitable means are used to prevent its diffusion in the case of multilayer coatings. Special dispersing agents may be used for incorporating the coupler compound in the emulsion and in certain cases the coupler may be absorbed or adsorbed to. the sensitive salt or than the amines themselves. Suitable compounds are diethyl-pphenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride and 2 amino fi-diethylaminotoluene hydrochloride. The p-amino phenols and their substitution products may also be used where the amino group is unsubstituted. All of, these developers have an unsubstituted aminogroup which enables the oxidation products of the developer to couple with the color forming compounds to form a dye image.

Our development process may be employed for the production of colored photographic images in layers oi gelatin or other carriers, such as collodion, organic esters of cellulose, or synthetic resins. The carrier may be supported by a transparent medium such as glass, a cellulose ester or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support I or as superposed layers on one or both sides of the support. The superposed layers may be diilerentially sensitized and the dyes formed therein by coupling may be bleached by an oxidizing agent such as chromic acid to colorless solubie compounds. The destruction of the dye in this way does not destroy the silver image and a silver image may be developed, bleached and deagent and a coupler compound having the formula:

u in which R is selected from the classconsisting of alkyl groups and aryl groups, R. is selected from the class consisting of hydrogen, alkyl and acyl 2. A color forming photographic developer comprising a primary aromatic amino developing agentand a coupler compound having the formula:

in which R is an aryl group'and R is selected irom the class consisting of hydrogen and acyl groups.

comprising a primary aromatic amino developing v3. A color forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound having the formula:

in which R is anaryl group.

4. A color .forming photographic developer Comprising a primary aromatic amino dveloping agent and a coupler compound having the following formula;

5. A color forming photographic developer comprising a primary aromatic aminodeveloping agent and a coupler compound having the following formula:

6. A color forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound having the following formula:

7. The method of producing a magenta colored photographic image in a gelatino-silver 2 halide emulsion layer which. comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:

in which R-is selected from the class consisting of alkyl groups and aryl groups, R. is selected from the class consisting of hydrogen, alkyl and acyl groups.

photographic image in a gelatino-siiver halide emulsion layer which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence oi! a coupler compound having the formula:

in which Ris an aryl' group and R is selected from the class consisting of hydrogen and acylgroups. r

8. The method of producing a magenta colored 4 s I I 22,329 i 9. Aphobozraphic emulsion for forming colored cred images comprising a colloidal carrier conimagescomprisingacolloidal carrier contsininga taming a. sensitive silver halide and a, coupler sensitive silver halide and a. coupler compound compound having the formula: having the formula: Y

N=C-NH-R 5 in which R is selected from the class consisting of from the class consisting of hydrogen and my alkyl groups and aryl groups, R is selected i'rom groups. r

the class consisting of hydrogen. alkyl and acyl HENRY D. PORTER. i

r ups. ARNOLD .nn.

10. A'photographic emulsion for forming col- 10 in which R is an M71 group and R islelccted' 

